US20040122270A1 - In-situ polymerization of monoethylenically unsaturated monomers with secondary amines - Google Patents
In-situ polymerization of monoethylenically unsaturated monomers with secondary amines Download PDFInfo
- Publication number
- US20040122270A1 US20040122270A1 US10/732,592 US73259203A US2004122270A1 US 20040122270 A1 US20040122270 A1 US 20040122270A1 US 73259203 A US73259203 A US 73259203A US 2004122270 A1 US2004122270 A1 US 2004122270A1
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- United States
- Prior art keywords
- group
- polymerization
- process according
- mixture
- member selected
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 title claims description 50
- 150000003335 secondary amines Chemical class 0.000 title description 15
- 238000011065 in-situ storage Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- -1 amino, hydroxy Chemical group 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 29
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 16
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012425 OXONE® Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 3
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 3
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical class CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 11
- 229920001400 block copolymer Polymers 0.000 abstract description 6
- 229920005604 random copolymer Polymers 0.000 abstract description 4
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 239000004342 Benzoyl peroxide Substances 0.000 description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical compound [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 150000002832 nitroso derivatives Chemical class 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 4
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 4
- 0 [4*]N([5*])[H] Chemical compound [4*]N([5*])[H] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004442 gravimetric analysis Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OKRSVCKJPLEHEY-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) acetate Chemical compound CC(=O)OC1CC(C)(C)NC(C)(C)C1 OKRSVCKJPLEHEY-UHFFFAOYSA-N 0.000 description 2
- ZAHPSFHHFNVYAR-UHFFFAOYSA-N 1,1,3,3-tetramethyl-2h-isoindole Chemical compound C1=CC=C2C(C)(C)NC(C)(C)C2=C1 ZAHPSFHHFNVYAR-UHFFFAOYSA-N 0.000 description 2
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 2
- TUGPREKSTXAQBY-UHFFFAOYSA-N 2,6-diethyl-2,3,6-trimethylpiperidin-4-ol Chemical compound CCC1(C)CC(O)C(C)C(C)(CC)N1 TUGPREKSTXAQBY-UHFFFAOYSA-N 0.000 description 2
- TUOLXKNMFCOMGN-UHFFFAOYSA-N 2,6-diethyl-2,3,6-trimethylpiperidin-4-one Chemical compound CCC1(C)CC(=O)C(C)C(C)(CC)N1 TUOLXKNMFCOMGN-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- LMQJZPNTLDBCHC-UHFFFAOYSA-N 1,1,3,3-tetraethyl-2h-isoindole Chemical compound C1=CC=C2C(CC)(CC)NC(CC)(CC)C2=C1 LMQJZPNTLDBCHC-UHFFFAOYSA-N 0.000 description 1
- WNGJCVHWVCNYHU-UHFFFAOYSA-N 1,1,3,3-tetrapropyl-2h-isoindole Chemical compound C1=CC=C2C(CCC)(CCC)NC(CCC)(CCC)C2=C1 WNGJCVHWVCNYHU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- MAVJJNYSENQROG-UHFFFAOYSA-N 14-oxa-7-azadispiro[5.1.5^{8}.2^{6}]pentadecane Chemical compound N1C2(CCCCC2)COC21CCCCC2 MAVJJNYSENQROG-UHFFFAOYSA-N 0.000 description 1
- HKNQNRDBGNRLRT-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-oxazolidine Chemical compound CC1(C)COC(C)(C)N1 HKNQNRDBGNRLRT-UHFFFAOYSA-N 0.000 description 1
- PIFBMJMXJMZZRG-UHFFFAOYSA-N 2,2,4,6,6-pentamethyl-1,5-dihydropyrimidine Chemical compound CC1=NC(C)(C)NC(C)(C)C1 PIFBMJMXJMZZRG-UHFFFAOYSA-N 0.000 description 1
- UTBLRYZTSZCMEY-UHFFFAOYSA-N 2,2,4-trimethyl-4-nitrosopentane Chemical compound CC(C)(C)CC(C)(C)N=O UTBLRYZTSZCMEY-UHFFFAOYSA-N 0.000 description 1
- HBXXWSVJRAXUDM-UHFFFAOYSA-N 2,5-dimethyl-2,5-diphenylpyrrolidine Chemical compound N1C(C)(C=2C=CC=CC=2)CCC1(C)C1=CC=CC=C1 HBXXWSVJRAXUDM-UHFFFAOYSA-N 0.000 description 1
- QRKXFWVNSSUMTA-UHFFFAOYSA-N 2,5-dimethyl-2,5-diphenylpyrrolidine-3-carboxylic acid Chemical compound N1C(C)(C=2C=CC=CC=2)CC(C(O)=O)C1(C)C1=CC=CC=C1 QRKXFWVNSSUMTA-UHFFFAOYSA-N 0.000 description 1
- ITUZAAYHAPMLCR-UHFFFAOYSA-N 2,6-diethyl-2,6-dimethylpiperidine Chemical compound CCC1(C)CCCC(C)(CC)N1 ITUZAAYHAPMLCR-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical class OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical class OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- PGMMQIGGQSIEGH-UHFFFAOYSA-N 2-ethenyl-1,3-oxazole Chemical class C=CC1=NC=CO1 PGMMQIGGQSIEGH-UHFFFAOYSA-N 0.000 description 1
- JDCUKFVNOWJNBU-UHFFFAOYSA-N 2-ethenyl-1,3-thiazole Chemical class C=CC1=NC=CS1 JDCUKFVNOWJNBU-UHFFFAOYSA-N 0.000 description 1
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical class C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical class C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- ZDHWTWWXCXEGIC-UHFFFAOYSA-N 2-ethenylpyrimidine Chemical class C=CC1=NC=CC=N1 ZDHWTWWXCXEGIC-UHFFFAOYSA-N 0.000 description 1
- HQWDKLAIDBOLFE-UHFFFAOYSA-M 2-fluoro-1-methylpyridin-1-ium;4-methylbenzenesulfonate Chemical compound C[N+]1=CC=CC=C1F.CC1=CC=C(S([O-])(=O)=O)C=C1 HQWDKLAIDBOLFE-UHFFFAOYSA-M 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- CUTWSDAQYCQTGD-UHFFFAOYSA-N 2-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)C(C)OC(=O)C=C CUTWSDAQYCQTGD-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CYOQIJLIDJSXET-IMVLJIQESA-N C=1C=CC=CC=1C1(C=2C=CC=CC=2)NC2=CC=CC=C2\C1=N/C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C1(C=2C=CC=CC=2)NC2=CC=CC=C2\C1=N/C1=CC=CC=C1 CYOQIJLIDJSXET-IMVLJIQESA-N 0.000 description 1
- WIVTXBIFTLNVCZ-UHFFFAOYSA-N CC(=C)C(=O)OCCP(=O)=O Chemical compound CC(=C)C(=O)OCCP(=O)=O WIVTXBIFTLNVCZ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005262 alkoxyamine group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- YICDLGHIRXZGFF-UHFFFAOYSA-N butanedioic acid;2,2,6,6-tetramethylpiperidine Chemical compound OC(=O)CCC(O)=O.CC1(C)CCCC(C)(C)N1.CC1(C)CCCC(C)(C)N1 YICDLGHIRXZGFF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- FFHWGQQFANVOHV-UHFFFAOYSA-N dimethyldioxirane Chemical compound CC1(C)OO1 FFHWGQQFANVOHV-UHFFFAOYSA-N 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical group C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- XMZBBIKROABUOG-UHFFFAOYSA-N hexanedioic acid;2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1.CC1(C)CCCC(C)(C)N1.OC(=O)CCCCC(O)=O XMZBBIKROABUOG-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- LUHVDTAFHFQDDZ-UHFFFAOYSA-N n-tert-butyl-1-dibutoxyphosphoryl-2,2-dimethylpropan-1-amine Chemical compound CCCCOP(=O)(C(NC(C)(C)C)C(C)(C)C)OCCCC LUHVDTAFHFQDDZ-UHFFFAOYSA-N 0.000 description 1
- BPRUOSQOAOIBDY-UHFFFAOYSA-N n-tert-butyl-1-diethoxyphosphoryl-2,2-dimethylpropan-1-amine Chemical compound CCOP(=O)(OCC)C(NC(C)(C)C)C(C)(C)C BPRUOSQOAOIBDY-UHFFFAOYSA-N 0.000 description 1
- ZYGVMFGUBUQYRF-UHFFFAOYSA-N n-tert-butyl-1-diethylphosphoryl-2,2-dimethylpropan-1-amine Chemical compound CCP(=O)(CC)C(C(C)(C)C)NC(C)(C)C ZYGVMFGUBUQYRF-UHFFFAOYSA-N 0.000 description 1
- YQZHVFUFITWNMO-UHFFFAOYSA-N n-tert-butyl-1-dipropoxyphosphoryl-2,2-dimethylpropan-1-amine Chemical compound CCCOP(=O)(OCCC)C(NC(C)(C)C)C(C)(C)C YQZHVFUFITWNMO-UHFFFAOYSA-N 0.000 description 1
- DMGKKRIEFYGCGV-UHFFFAOYSA-N n-tert-butyl-1-dipropylphosphoryl-2,2-dimethylpropan-1-amine Chemical compound CCCP(=O)(CCC)C(NC(C)(C)C)C(C)(C)C DMGKKRIEFYGCGV-UHFFFAOYSA-N 0.000 description 1
- FVHSUDLWWSRVOL-UHFFFAOYSA-N n-tert-butyl-2-methyl-1-phenylpropan-1-amine Chemical compound CC(C)(C)NC(C(C)C)C1=CC=CC=C1 FVHSUDLWWSRVOL-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- QDQYEYNEWLDWNZ-UHFFFAOYSA-N phthalic acid;2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1.CC1(C)CCCC(C)(C)N1.OC(=O)C1=CC=CC=C1C(O)=O QDQYEYNEWLDWNZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/26—Nitrogen
- C08F12/28—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
Definitions
- the present invention relates to a polymerization process and more particularly to a process entailing no additional free-radical initiator.
- a process for the preparation of any of well-defined homopolymers, random and block copolymers is disclosed.
- the process that entails forming a mixture of monomers, a hindered secondary amine and an oxidizing agent is characterized in the absence of any additional free-radical initiator.
- radical polymerization due to the far less demanding conditions, i.e. the possible use of water as solvent, the far broader temperature range which can be employed as well as the broader range of monomers which can be polymerized.
- radical copolymerization offers many opportunities for modifying the polymer properties.
- the neutrality of the radical species is however responsible for irreversible transfer and termination reactions, which are responsible for the poor control of the macromolecular structures including degree of polymerization, polymolecularity, end functionality and chain architecture.
- controlled radical polymerization is a powerful tool for controlling finely the molecular characteristics of the chains (M n , M w /M n ) and their macromolecular architecture.
- CRP controlled radical polymerization
- well-defined block copolymers can be synthesized by the sequential addition of comonomers and polymers with terminal functional groups can be made available by the judicious choice of either the initiator ( ⁇ -chain-end) or the deactivating agent ( ⁇ -chain-end).
- NMP nitroxyl-mediated polymerization
- U.S. Pat. No. 6,320,007 and JP-A 08208714 describe the manufacture of thermoplastic polymers having narrow molecular weight distribution using an in situ NMP process, in which the stable nitroxyl radical is formed from a precursor substance in a reactor.
- the polymerization process occurs in two steps: firstly the nitroxyl radicals are formed from the precursor (secondary amine) and secondly, the nitroxyl radical is added to the polymerization of the vinyl monomer in order to form a thermoplastic polymer characterized by a narrow molecular weight distribution.
- TMP 2,2,6,6-tetramethylpiperidine
- m-chloroperbenzoic acid or a mixture of hydrogen peroxide and sodium tungstate as the oxidizing agent.
- Drawbacks of these processes are the long reaction times to form the nitroxyl radical prior to polymerization and the use of free-radical initiators (such as benzoyl peroxide for instance) to initiate the polymerization, which makes a preliminary reaction between the monomer, the initiator and the nitroxyl radical necessary before polymerization. This is associated with an increase in the cost of the process.
- the object of the present invention was to provide a new pathway for the synthesis of homo- and copolymers of controlled molecular weight and controlled molecular structure. Such a process should be a simple and inexpensive method of controlling the free-radical polymerization of vinyl monomers that overcomes the drawbacks encountered in the prior art.
- the object of the present invention is a process for producing of oligomers, cooligomers, polymers or block or random copolymers comprising
- R 1 , R 2 , R 3 are independently selected from the group consisting of hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -cycloalkyl C 6 -C 24 -aryl, halogen, cyano, C 1 -C 20 -alkylester C 1 -C 20 -cycloalkylester, C 1 -C 20 -alkylamide, C 1 -C 20 -cycloalkylamide C 6 -C 24 -arylester or C 6 -C 24 -arylamide,
- R 4 and R 5 are independently selected from the group consisting of C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 12 -cycloalkyl or C 3 -C 12 -heterocycloalkyl, C 6 -C 24 -aryl, which are unsubstituted or substituted by NO 2 , halogen, amino, hydroxy, cyano, carboxy, ester, ketone, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylamino; and C 4 -C 12 -alkanol; or
- R 4 and R 5 optionally form, together with the intermediate nitrogen atom linking them a C 2 -C 13 -heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
- R 4 and R 5 together form a residue of a polycyclic ring system or a polycyclic heterocycloaliphatic ring system containing oxygen, sulfur or nitrogen atoms;
- C 8 -C 16 -ethylenically unsaturated phenolic compounds which may also be used as comonomers are 4-hydroxystyrene, 4-hydroxy, ⁇ -methyl styrene, 2,6-ditert-butyl and 4-vinyl phenol.
- carboxylic acid monomers suitable for use as comonomers in this invention are C 4 -C 6 -ethylenically unsaturated dicarboxylic acids and the alkali metal and ammonium salts thereof as well as the anhydrides of cis-dicarboxylic acids.
- Examples include maleic acid, maleic anhydride, itaconic acid, mesaconic acid, fumaric acid and citraconic acid.
- Maleic anhydride and itaconic acid are the preferred monoethylenically unsaturated dicarboxylic acid monomers.
- the acid monomers suitable for use in the present invention may be in the form of their acids or in the form of the alkali metal salts or ammonium salts of the acid.
- Particularly preferred monomers are styrene, substituted styrene, vinyl acetate, acrylonitrile, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and maleic anhydride.
- Suitable oxidizing agents (A) are all oxidizing agents known in the art for the oxidation of secondary amines into nitroxyl radicals.
- Preferred oxidizing agents are peracids such as peracetic acid, perpropionic acid, m-chloro-perbenzoic acid, dimethyldioxirane, perbenzoic acid, or peroxides such as potassium peroxymonosulfate (2 KHSO 5 .KHSO 4 .K 2 SO 4 , Oxone®, DuPont Specialty Chemistry, USA), hydrogen peroxide, hydrogen peroxide/sodium tungstate, hydrogen peroxides/titanium containing catalysts, such as for example titanium dioxide and titanium silicalites (EP-A 0 488 403, page 5), dibenzoyl peroxide phosphotungstic acid and oxidizing gases such as molecular oxygen or ozone.
- peracids such as peracetic acid, perpropionic acid, m-chloro-perbenz
- Metal oxides such as silver oxide, lead (IV) oxide and sodium tungstate may also be used, optionally in combination with another oxidizing agent. A mixture of various oxidizing agents may also be used.
- peracetic acid perpropionic acid
- hydrogen peroxide hydrogen peroxide/titanium containing catalysts
- potassium peroxymonosulfate (2 KHSO 5 .KHSO 4 .K 2 SO 4 )
- dibenzoyl peroxide silver oxide and lead (IV) oxide.
- Suitable sterically hindered secondary amines of the general formula (I) include those of the following formulae (II) to (VIII):
- each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 independently one of the others is a member selected from the group consisting of hydrogen, halogen or cyano-, amide-, ether-, ester-, thioether-, ketone-, amide-, carbomyl-, amidine- or dialkylphosphonyl-containing groups; or
- R 6 to R 19 are each independently is a member selected form the group consisting of C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 12 -cycloalkyl or C 3 -C 12 -heterocycloalkyl, C 6 -C 24 -aryl, which are unsubstituted or substituted by NO 2 , halogen, amino, hydroxy, cyano, carboxy, ester, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylamino; or
- R 6 to R 19 form, together with the intermediate carbon atom linking them, a C 3 -C 12 -cycloalkyl residue, a C 4 -C 12 -alkanol residue or a C 2 -C 13 -hetero-cycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
- At least one of the residues R 6 to R 19 contains a functional group Y which is capable of reacting further or of cross-linking with functional groups known in the coatings field and is for example hydroxyl, carboxylate or amino groups.
- Y is a hydroxyl group.
- X represents a methylene, ketone, ester group or oxygen atom, or a hydrocarbon residue, which may be substituted by a cyano, ester, hydroxy, nitro, ether or imido group.
- R 20 is a member selected from the group consisting of C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 12 -cycloalkyl or C 3 -C 12 -heterocycloalkyl, C 6 -C 24 aryl, which are unsubstituted or substituted by NO 2 , halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio and C 1 -C 4 -alkylamino;
- R 20 optionally contains a functional group Y which is capable of reacting further or of crosslinking with the functional groups known from the coatings field; and is for example hydroxyl, carboxylate, or amino groups.
- Y is a hydroxyl group.
- R 21 and R 22 independently one of the other is a member selected from the group consisting of hydrogen, halogen and cyano-, amide-, ether-, ester-, thioether-, ketone-, amide-, carbomyl-, amidine- or alkylphosphonyl-containing groups; preferably
- R 21 and R 22 independently one of the other is a member selected from the group consisting of C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 12 -cycloalkyl or C 3 -C 12 -heterocycloalkyl, C 6 -C 24 -aryl, which are unsubstituted or substituted by NO 2 , halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio and C 1 -C 4 -alkylamino; or
- R 21 and R 22 optionally form, together with the carbon atom linking them, a C 3 -C 12 -cycloalkyl residue, a C 4 -C 12 -alkanol residue or a C 2 -C 13 -heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
- R 21 and R 22 together with the carbon atom linking them, form a polycyclic ring system or a polycyclic heterocycloaliphatic ring system containing oxygen, sulfur or nitrogen atoms;
- R 23 and R 24 optionally form, together with the intermediate phosphorus atom linking them, a C 2 -C 13 -heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms;
- residues R 20 to R 24 contains a functional group Y which is capable of further reacting or of crosslinking with functional groups known from the coatings field;
- R 23 and R 24 form, together with the intermediate phosphorus atom, a C 3 -C 12 -cycloalkyl residue, a C 4 -C 12 -alkanol residue or a C 2 -C 13 -heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms;
- residues R 23 to R 24 optionally contains a functional group Y which is capable of further reacting or of crosslinking with functional groups known from the coatings field, and is for example hydroxyl, carboxylate, or amino groups.
- Y is a hydroxyl group.
- Preferred secondary amines of the general formula (I) are tert-butyl amine; 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetra-methyl-4-piperidinone; 2,2,6,6-tetramethyl-4-piperidinyl acetate; 2,2,6,6-tetra-methyl-4-piperidinyl stearate; 2,2,6,6-tetrarnethyl-4-piperidinyl benzoate; 2,6-dimethyl-2,6-diethylpiperidine; diethyl 1-(tert-butylamino)-2,2-dimethylpropyl-phosphonate; dipropyl 1-(tert-butylamino)-2,2-dimethylpropylphosphonate; dibutyl 1-(tert-butylamino)-2,2-dimethylpropylphosphonate; dibuty
- Particularly preferred secondary amines of the general formula (I) are tert-butyl amine; 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetramethyl-4-piperidinone; 2,2,6,6-tetramethyl-4-piperidinyl acetate; diethyl 1-(tert-butylamino)-2,2-dimethylpropyl phosphonate; dipropyl 1-(tert-butylamino)-2,2-dimethylpropyl phosphonate; dibutyl 1-(tert-butylamino)-2,2-dimethylpropyl phosphonate; 2,6-diethyl-2,3,6-trimethyl-4-piperidinone; 2,6-diethyl-2,3,6-trimethyl-4-piperidinol; 2,2,5,5-tetramethyl-1-pyrrolidine and 1,1,3,3-tetramethylisoindoline.
- Polyfunctional amines may also be used as compounds of the formula (I).
- polyfunctional amines are compounds which have more than one secondary amino group. These properties are particularly recommended in the instances where low viscosity of the polymer is required during processing.
- polyfunctional amines are bis(2,2,6;6-tetramethylpiperidine) sebacate; bis(2,2,6,6-tetramethylpiperidine) succinate; bis(2,2,6,6-tetramethylpiperidine) adipate; bis(2,2,6,6-tetramethylpiperidine) phthalate; bis(2,2,6,6-tetramethylpiperidine) isophtalate; bis(2,2,6,6-tetramethylpiperidine) terephtalate; or polymeric multifunctional amines such as poly((6-((1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidinyl)imino)-1,6-hexanediyl-((2,2,6,6-tetramethyl-4-piperidinyl)imino)) (CHIMASSORB® 944,
- the secondary amine and oxidizing agent are introduced in a quantity ranging from about 30 wt. % to about 0,01 wt. %, preferably from about 10 wt. % to about 0,05 wt. % and more preferably from about 5 wt. % to about 0,06 wt. %, based on the weight of the monomer(s).
- polymerization occurs by heating the mixture of the first step at a temperature ranging from about 0° C. to about 220° C., preferably from about 50° C. to about 180° C. and most preferably from about 70° C. to about 150° C.
- the second step of the process of the present invention is generally carried out in an inert gas atmosphere such as nitrogen or argon.
- the reaction time may range from about 10 minutes to about 72 h, preferably from about 30 minutes to about 32 h, and more preferably from about 1 h to about 24 h.
- Another method of carrying out the invention is to heat a mixture of at least one secondary amine of the general formula (I), at least one oxidizing agent (A) and at least one vinyl monomer (M) in a single step.
- the temperature ranges from about 0° C. to about 220° C., preferably from about 50° C. to about 180° C. and most preferably from about 70° C. to about 150° C.
- Polymerization is generally carried out in an inert gas atmosphere such as nitrogen or argon.
- the reaction time ranges from about 10 minutes to about 72 h, preferably from about 30 minutes to about 32 h and more preferably from about 1 h to about 24 h.
- additives may be added to the polymerization medium before the polymerization or during the polymerization process in order to accelerate the polymerization.
- additives are well-known in the art and are for example camphorsulfonic acid, 2-fluoro-1-methylpyridinium p-toluenesulfonate, acylating compounds such as acetic anhydride (Tetrahedron 1997, 53(45), 15225), glucose, dextrose (Macromolecules 1998, 31, 7559), ascorbic acid (Macromolecules 2001, 34, 6531) or long-life radical initiators as reported in U.S. Pat. No. 6,288,186 (column 4, lines 8-24).
- the polymers prepared according to the present invention show a low polydispersity (M w /M n ) which is usually lower than 2 and preferably below 1.5.
- the (co)polymers of the present invention may have a number average molecular weight of from 500 to 2 ⁇ 10 6 , preferably from 2000 to 5 ⁇ 10 5 and more preferably from 2000 to 2.5 ⁇ 10 5 .
- the number average molecular weight of the polymer chains increases linearly with the monomer conversion, which allows a tailor-made polymer molecular weight to be obtained.
- the molecular weight of the polymers may be controlled by varying the amount of secondary amine(s) and/or oxidizing agent(s) in relation to the amount of monomers. High molecular weight polymers may be formed.
- a further advantage of the present invention is that, after the removal of the non-polymerized monomers from the (co)polymers or after reaching a conversion rate of approximately 100%, a second polymerization step may be initiated simply by adding to the polymer synthesized in the first step a portion of fresh vinyl monomer or monomer mixture that may be different from the vinyl monomer or monomer mixture used in the first polymerization step.
- the polymerization of the vinyl monomer or monomer mixture added in the second step is then initiated by the polymer chains synthesized in the first polymerization step and di-block copolymers may for example be produced if the polymer chains synthesized in the first polymerization step consist of linear chains with one single growing chain end.
- the molecular weight and polydispersity of each block may be controlled independently during the respective polymerization step. This process may be repeated several times and may then provide multiblock copolymers of controlled molecular weight and molecular weight distribution for each block.
- the resulting polymers are usually colorless and may be used in most cases without any further purification for the production of coatings, elastomers, adhesives, plastics and compatibilizers in thermoplastic blends.
- the molecular weight was determined by gel permeation chromatography (GPC) using a Shodex RI 74 differential refractometer. A flow rate of 1 ml/min was used and samples were prepared in THF. Polystyrene standards were used for calibration.
- Example 1 of U.S. Pat. No. 6,320,007 describes the polymerization of styrene in the presence of 2,2,6,6-tetramethylpiperidine, m-chloroperbenzoic acid (mCPBA) and benzoyl peroxide (BPO) in a three-step process:
- mCPBA m-chloroperbenzoic acid
- BPO benzoyl peroxide
- controlled polymerization occurs by increasing the polymerization temperature to 123° C.
- Example 1 of U.S. Pat. No. 6,320,007 is converted into a one-pot process (all the reagents being added at the beginning of the process), no evolution of the molecular weight with the monomer conversion and broad polydispersity are observed. Additionally, uncontrolled polymerization already occurs when the reaction medium is heated to 95° C.
- the mixture is stirred at room temperature in a water bath and degassed by bubbling through argon for 10 minutes. After 30 minutes at room temperature, the mixture is heated at 110° C. for 1 h, and then at 140° C. Samples are withdrawn from the polymerization medium after 4 and 6 h for analysis. After elimination of the residual monomer, the polymer is dried at 70° C. in vacuo for 24 h.
- the increase in the molecular weight of the polymer with the monomer conversion is indicative of a controlled process.
Abstract
A process for the preparation of any of well-defined homopolymers, random and block copolymers is disclosed. The process that entails forming a mixture of monomers, a hindered secondary amine and an oxidizing agent is characterized in the absence of any additional free-radical initiator.
Description
- The present invention relates to a polymerization process and more particularly to a process entailing no additional free-radical initiator.
- A process for the preparation of any of well-defined homopolymers, random and block copolymers is disclosed. The process that entails forming a mixture of monomers, a hindered secondary amine and an oxidizing agent is characterized in the absence of any additional free-radical initiator.
- Today, the demand for homopolymers, random copolymers and block copolymers of a specific molecular weight, narrow molecular weight distribution and/or well-defined end groups has continuously increased in a number of industries. The controlled structure of these macromolecules provides them with novel properties and allows a tailor-made property profile to be obtained. Many new technologies require controlled polymer structures such as for instance in the fields of electronics, computer science, communications, genetic engineering, biotechnology and materials science.
- Many polymers are commercially produced by free radical polymerization due to the far less demanding conditions, i.e. the possible use of water as solvent, the far broader temperature range which can be employed as well as the broader range of monomers which can be polymerized. Moreover, radical copolymerization offers many opportunities for modifying the polymer properties. The neutrality of the radical species is however responsible for irreversible transfer and termination reactions, which are responsible for the poor control of the macromolecular structures including degree of polymerization, polymolecularity, end functionality and chain architecture.
- On the other hand, controlled radical polymerization (CRP) is a powerful tool for controlling finely the molecular characteristics of the chains (Mn, Mw/Mn) and their macromolecular architecture. For example, well-defined block copolymers can be synthesized by the sequential addition of comonomers and polymers with terminal functional groups can be made available by the judicious choice of either the initiator (α-chain-end) or the deactivating agent (ω-chain-end).
- Of all the CRP systems presently under investigation, nitroxyl-mediated polymerization (NMP) is one of the most efficient. This process is based on the reversible capture of the propagating radicals by nitroxyl radicals to form dormant chains. This approach is for example disclosed in U.S. Pat. No. 4,581,429. Nevertheless, this NMP process is handicapped by slow polymerization kinetics, a limited range of suitable monomers and the high cost of the required nitroxyl radicals.
- Quite recently, some of these NMP problems have been solved. Both the acceleration of the rate of polymerization and the broadening of the range of monomers to be polymerized have been reported by Hawker et al. (J. Am. Chem. Soc. 1999, 121, 3904) and for example in WO-A 96/24620. Reduced polymerization temperatures have been reported by Miura et al. (Macromolecules 2001, 34, 447) by using nitroxyl radicals with spiro structures.
- Although these improved NMP processes represent attractive methods for obtaining new polymer structures, they still require the use of not readily available and complicated nitroxyl radicals and/or alkoxyamines, which considerably increase the total cost of a technical process. Consequently, there is still a need for more simple NMP processes able for polymerizing a broad range of monomers.
- WO-A 99/03894 and U.S. Pat. No. 6,262,206 disclose the use of nitrones and nitroso compounds to control the radical polymerization of vinyl monomers. When these compounds were added to the radical polymerization of vinyl monomers, nitroxyl radicals were formed in-situ by reaction of the initiating radicals or propagating chains with the nitrones or nitroso compounds. The polymerization was thus controlled by an NMP mechanism.
- The use of nitrones and nitroso compounds for promoting the free radical polymerization of vinyl monomers controlled by an in situ NMP process has also been reported for example by D. F. Grishin et al.,Polymer Science, Ser. A, 1999, 41(4), 401; D. F. Grishin et al, Polymer Science, Ser. B. 2000 42(7-8), 189; D. F. Grishin et al., Russian Journal ofApplied Chemistry 2001, 74(3), 494; D. F. Grishin et al. Mendeleev Commun. 1999, 250; D. F. Grishin et al., Russian Journal ofApplied Chemistry 2001, 74(9), 1594.
- More recently, the controlled radical polymerization of styrene mediated by nitroso-tert-octane was reported by J. M. Catala et al.,Macromolecules 2001, 34, 8654.
- These in-situ processes using nitroso compounds or nitrones allow the avoidance of the tedious synthesis of the nitroxyl radicals. Nevertheless, these methods require the use of preformed reagents which may be toxic (especially in case of nitroso compounds), and most of them are still not readily available and have to be synthesized by special methods.
- U.S. Pat. No. 6,320,007 and JP-A 08208714 describe the manufacture of thermoplastic polymers having narrow molecular weight distribution using an in situ NMP process, in which the stable nitroxyl radical is formed from a precursor substance in a reactor. The polymerization process occurs in two steps: firstly the nitroxyl radicals are formed from the precursor (secondary amine) and secondly, the nitroxyl radical is added to the polymerization of the vinyl monomer in order to form a thermoplastic polymer characterized by a narrow molecular weight distribution. In the two examples, 2,2,6,6-tetramethylpiperidine (TMP) is used as precursor for the nitroxyl radical, when combined with m-chloroperbenzoic acid or a mixture of hydrogen peroxide and sodium tungstate as the oxidizing agent. Drawbacks of these processes are the long reaction times to form the nitroxyl radical prior to polymerization and the use of free-radical initiators (such as benzoyl peroxide for instance) to initiate the polymerization, which makes a preliminary reaction between the monomer, the initiator and the nitroxyl radical necessary before polymerization. This is associated with an increase in the cost of the process.
- The object of the present invention was to provide a new pathway for the synthesis of homo- and copolymers of controlled molecular weight and controlled molecular structure. Such a process should be a simple and inexpensive method of controlling the free-radical polymerization of vinyl monomers that overcomes the drawbacks encountered in the prior art.
- Surprisingly, it has now been found that it is possible to provide a process for the preparation of well-defined (co)polymers of controlled molecular weight, narrow polydispersity, high monomer conversion and controlled architecture, at relatively low temperatures and with short reaction times, if the polymerization of vinyl monomers is carried out in the presence of a secondary amine and an oxidizing agent. The addition of a free radical initiator before polymerization is unnecessary. Moreover, no preliminary reaction between the secondary amine and the oxidizing agent is required prior to the addition of the monomer(s), and the polymerization medium can be quite rapidly heated at the polymerization temperature without any preliminary reaction of the products.
- The object of the present invention is a process for producing of oligomers, cooligomers, polymers or block or random copolymers comprising
- (I) forming a mixture that includes
- a) at least one monoethylenically unsaturated monomer of the general formula (M),
- HR1C═CR2R3 (M),
- wherein
- R1, R2, R3 are independently selected from the group consisting of hydrogen, C1-C20-alkyl, C1-C20-cycloalkyl C6-C24-aryl, halogen, cyano, C1-C20-alkylester C1-C20-cycloalkylester, C1-C20-alkylamide, C1-C20-cycloalkylamide C6-C24-arylester or C6-C24-arylamide,
- b) at least one oxidizing agent (A) and
-
- wherein
- R4 and R5 are independently selected from the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl or C3-C12-heterocycloalkyl, C6-C24-aryl, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, ester, ketone, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino; and C4-C12-alkanol; or
- R4 and R5 optionally form, together with the intermediate nitrogen atom linking them a C2-C13-heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
- R4 and R5 together form a residue of a polycyclic ring system or a polycyclic heterocycloaliphatic ring system containing oxygen, sulfur or nitrogen atoms;
- wherein the carbon atom of the R4 and R5 radicals directly adjacent to the nitrogen atom is in each case substituted by 2 or 3 further organic substituents;
- wherein optionally at least one of the residues R4 and R5 contain a functional group Y which is capable of further reacting or crosslinking with functional groups known in the coatings field, and is for example hydroxyl, carboxylate, or amino groups. Preferably Y is a hydroxyl group.
- (II) heating the mixture to a temperature of about 0 to 220° C.
- Monoethylenically unsaturated monomers (M) suitable for the present invention include the alkyl esters of acrylic or methacrylic acids, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate; the hydroxyalkyl esters of acrylic or methacrylic acids, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; acrylamide, methacrylamide, N-tertiary butylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide; acrylonitrile, methacrylonitrile, allyl alcohol, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, vinyl acetate, conjugated dienes such as butadiene or isoprene, styrene, styrenesulfonic acid salts, vinylsulfonic acid salts and 2-acrylamido-2-methylpropane-sulfonic acid salts and acryloyl. Suitable monomers may be water-soluble or water-insoluble.
- Examples of comonomers suitable for use in the present invention are C3-C6-ethylenically unsaturated monocarboxylic acids as well as the alkali metal salts and ammonium salts thereof. The C3-C6-ethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid and acryloxypropionic acid. Acrylic acid and methacrylic acid are the preferred monoethylenically unsaturated monocarboxylic acid monomers.
- Examples of C8-C16-ethylenically unsaturated phenolic compounds which may also be used as comonomers are 4-hydroxystyrene, 4-hydroxy, α-methyl styrene, 2,6-ditert-butyl and 4-vinyl phenol.
- Another class of carboxylic acid monomers suitable for use as comonomers in this invention are C4-C6-ethylenically unsaturated dicarboxylic acids and the alkali metal and ammonium salts thereof as well as the anhydrides of cis-dicarboxylic acids. Examples include maleic acid, maleic anhydride, itaconic acid, mesaconic acid, fumaric acid and citraconic acid. Maleic anhydride and itaconic acid are the preferred monoethylenically unsaturated dicarboxylic acid monomers.
- The acid monomers suitable for use in the present invention may be in the form of their acids or in the form of the alkali metal salts or ammonium salts of the acid.
- Preferred comonomers are selected from the group consisting of (meth)acrylic acid esters of C1-C20-alcohols, acrylonitrile, cyanoacrylic acid esters of C1-C20-alcohols, maleic acid diesters of C1-C6-alcohols, maleic anhydride, vinylpyridines, vinyl(alkylpyrroles), vinyloxazoles, vinyloxazolines, vinylthiazoles, vinylimidazoles, vinylpyrimidines, vinyl ketones, conjugated dienes, acrolein, styrene or styrene derivatives which contain a C1-C6-alkyl radical or halogen in the α-position and contain up to 3 additional substituents on the aromatic ring.
- Particularly preferred monomers are styrene, substituted styrene, vinyl acetate, acrylonitrile, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and maleic anhydride.
- Suitable oxidizing agents (A) are all oxidizing agents known in the art for the oxidation of secondary amines into nitroxyl radicals. Preferred oxidizing agents are peracids such as peracetic acid, perpropionic acid, m-chloro-perbenzoic acid, dimethyldioxirane, perbenzoic acid, or peroxides such as potassium peroxymonosulfate (2 KHSO5.KHSO4.K2SO4, Oxone®, DuPont Specialty Chemistry, USA), hydrogen peroxide, hydrogen peroxide/sodium tungstate, hydrogen peroxides/titanium containing catalysts, such as for example titanium dioxide and titanium silicalites (EP-A 0 488 403, page 5), dibenzoyl peroxide phosphotungstic acid and oxidizing gases such as molecular oxygen or ozone.
- Metal oxides such as silver oxide, lead (IV) oxide and sodium tungstate may also be used, optionally in combination with another oxidizing agent. A mixture of various oxidizing agents may also be used.
- Particularly preferred are peracetic acid, perpropionic acid, hydrogen peroxide, hydrogen peroxide/titanium containing catalysts, potassium peroxymonosulfate (2 KHSO5.KHSO4.K2SO4), dibenzoyl peroxide, silver oxide and lead (IV) oxide.
-
- wherein
- each of R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 independently one of the others is a member selected from the group consisting of hydrogen, halogen or cyano-, amide-, ether-, ester-, thioether-, ketone-, amide-, carbomyl-, amidine- or dialkylphosphonyl-containing groups; or
- R6 to R19 are each independently is a member selected form the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl or C3-C12-heterocycloalkyl, C6-C24-aryl, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, ester, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino; or
- R6 to R19 form, together with the intermediate carbon atom linking them, a C3-C12-cycloalkyl residue, a C4-C12-alkanol residue or a C2-C13-hetero-cycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
- R6 to R19 together form a residue of a polycyclic ring system or a polycyclic heterocycloaliphatic ring system containing oxygen, sulfur or nitrogen atoms;
- wherein optionally at least one of the residues R6 to R19 contains a functional group Y which is capable of reacting further or of cross-linking with functional groups known in the coatings field and is for example hydroxyl, carboxylate or amino groups. Preferably Y is a hydroxyl group.
- X represents a methylene, ketone, ester group or oxygen atom, or a hydrocarbon residue, which may be substituted by a cyano, ester, hydroxy, nitro, ether or imido group.
-
- wherein
- R20 is a member selected from the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl or C3-C12-heterocycloalkyl, C6-C24aryl, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4-alkoxy, C1-C4-alkylthio and C1-C4-alkylamino;
- R20 optionally contains a functional group Y which is capable of reacting further or of crosslinking with the functional groups known from the coatings field; and is for example hydroxyl, carboxylate, or amino groups. Preferably, Y is a hydroxyl group.
- R21 and R22 independently one of the other is a member selected from the group consisting of hydrogen, halogen and cyano-, amide-, ether-, ester-, thioether-, ketone-, amide-, carbomyl-, amidine- or alkylphosphonyl-containing groups; preferably
- R21 and R22 independently one of the other is a member selected from the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl or C3-C12-heterocycloalkyl, C6-C24-aryl, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4-alkoxy, C1-C4-alkylthio and C1-C4-alkylamino; or
- R21 and R22 optionally form, together with the carbon atom linking them, a C3-C12-cycloalkyl residue, a C4-C12-alkanol residue or a C2-C13-heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
- R21 and R22 together with the carbon atom linking them, form a polycyclic ring system or a polycyclic heterocycloaliphatic ring system containing oxygen, sulfur or nitrogen atoms;
- wherein R23 and R24 optionally form, together with the intermediate phosphorus atom linking them, a C2-C13-heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms;
- wherein optionally at least one of the residues R20 to R24 contains a functional group Y which is capable of further reacting or of crosslinking with functional groups known from the coatings field;
- R23, R24 independently one of the other is a member selected from the group consisting of C1-C18-alkyl, C2-CIs8-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl or C3-C12-heterocycloalkyl or C6-C24-aryl, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino or a C4-C12-alkanol,
- wherein R23 and R24 form, together with the intermediate phosphorus atom, a C3-C12-cycloalkyl residue, a C4-C12-alkanol residue or a C2-C13-heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms;
- wherein at least one of the residues R23 to R24 optionally contains a functional group Y which is capable of further reacting or of crosslinking with functional groups known from the coatings field, and is for example hydroxyl, carboxylate, or amino groups.
- Preferably, Y is a hydroxyl group. Preferred secondary amines of the general formula (I) are tert-butyl amine; 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetra-methyl-4-piperidinone; 2,2,6,6-tetramethyl-4-piperidinyl acetate; 2,2,6,6-tetra-methyl-4-piperidinyl stearate; 2,2,6,6-tetrarnethyl-4-piperidinyl benzoate; 2,6-dimethyl-2,6-diethylpiperidine; diethyl 1-(tert-butylamino)-2,2-dimethylpropyl-phosphonate; dipropyl 1-(tert-butylamino)-2,2-dimethylpropylphosphonate; dibutyl 1-(tert-butylamino)-2,2-dimethylpropylphosphonate; N-(tert-butyl)-1 (diethyl-phosphoryl)-2,2-dimethyl-1-propylamine; N-(tert-butyl)-1-(dipropylphosphoryl)-2,2-dimethyl-1-propylamine; N-(tert-butyl)-2-methyl-1-phenyl-1-propylamine; 2,2,4,6,6-pentamethyl-1,2,5,6-tetrahydropyrimidine; N-[(3E)-2,2-diphenyl-1,2-dihydro-3H-indol-3-ylidene]-N-phenylamine; 2,6-diethyl-2,3,6-trimethyl-4-piperidinone; 2,6-diethyl-2,3,6-trimethyl-4-piperidinol; 14-oxa-7-azadispiro[5.1.5.2]pentadecane; 2,2,4,4-tetramethyl-1,3-oxazolidine; 2,2,5,5-tetramethyl-1-pyrrolidine; 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidine; 2,5-diphenyl-2,5-dimethylpyrrolidine; 3-carboxy-2,5-diphenyl-2,5-dimethylpyrrolidine; 1,1,3,3-tetraethylisoindoline; 1,1,3,3-tetramethylisoindoline; 1,1,3,3-tetrapropylisoindoline.
- Particularly preferred secondary amines of the general formula (I) are tert-butyl amine; 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetramethyl-4-piperidinone; 2,2,6,6-tetramethyl-4-piperidinyl acetate; diethyl 1-(tert-butylamino)-2,2-dimethylpropyl phosphonate; dipropyl 1-(tert-butylamino)-2,2-dimethylpropyl phosphonate; dibutyl 1-(tert-butylamino)-2,2-dimethylpropyl phosphonate; 2,6-diethyl-2,3,6-trimethyl-4-piperidinone; 2,6-diethyl-2,3,6-trimethyl-4-piperidinol; 2,2,5,5-tetramethyl-1-pyrrolidine and 1,1,3,3-tetramethylisoindoline.
- Polyfunctional amines may also be used as compounds of the formula (I). In the context of the present invention polyfunctional amines are compounds which have more than one secondary amino group. These properties are particularly recommended in the instances where low viscosity of the polymer is required during processing.
- Some examples of suitable polyfunctional amines are bis(2,2,6;6-tetramethylpiperidine) sebacate; bis(2,2,6,6-tetramethylpiperidine) succinate; bis(2,2,6,6-tetramethylpiperidine) adipate; bis(2,2,6,6-tetramethylpiperidine) phthalate; bis(2,2,6,6-tetramethylpiperidine) isophtalate; bis(2,2,6,6-tetramethylpiperidine) terephtalate; or polymeric multifunctional amines such as poly((6-((1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidinyl)imino)-1,6-hexanediyl-((2,2,6,6-tetramethyl-4-piperidinyl)imino)) (CHIMASSORB® 944, Ciba Specialty Chemicals, D-Lampertheim).
- One method of carrying out the invention is that in the first step at least one secondary amine of the general formula (I), at least one oxidizing agent (A) and at least one vinyl monomer (M) are mixed together. The temperature of the reaction may range from about −20° C. to about 150° C., preferably from about 0° C. to about 100° C. and more preferably from about 0° C. to about 50° C. The reaction time may range from about 1 minute to about 72 h, preferably from about 5 minutes to about 24 h, and more preferably from about 1.5 minutes to about 12 h. The first step of the process of the present invention can be carried out in air or in an inert gas atmosphere such as nitrogen or argon. The secondary amine and oxidizing agent are introduced in a quantity ranging from about 30 wt. % to about 0,01 wt. %, preferably from about 10 wt. % to about 0,05 wt. % and more preferably from about 5 wt. % to about 0,06 wt. %, based on the weight of the monomer(s).
- In the second step of the process, polymerization occurs by heating the mixture of the first step at a temperature ranging from about 0° C. to about 220° C., preferably from about 50° C. to about 180° C. and most preferably from about 70° C. to about 150° C. The second step of the process of the present invention is generally carried out in an inert gas atmosphere such as nitrogen or argon. The reaction time may range from about 10 minutes to about 72 h, preferably from about 30 minutes to about 32 h, and more preferably from about 1 h to about 24 h.
- Another method of carrying out the invention is to heat a mixture of at least one secondary amine of the general formula (I), at least one oxidizing agent (A) and at least one vinyl monomer (M) in a single step. The temperature ranges from about 0° C. to about 220° C., preferably from about 50° C. to about 180° C. and most preferably from about 70° C. to about 150° C. Polymerization is generally carried out in an inert gas atmosphere such as nitrogen or argon. The reaction time ranges from about 10 minutes to about 72 h, preferably from about 30 minutes to about 32 h and more preferably from about 1 h to about 24 h.
- In the process according to the invention it is preferred to use as few solvents as possible. If organic solvents are required, suitable solvents or mixtures of solvents are typically pure alkanes, such as hexane, heptane or cycloalkane, hydrocarbons, such as toluene, ethylbenzene or xylene, halogenated hydrocarbons, such as chlorobenzene, esters, such as ethyl acetate, propyl, butyl or hexyl acetate, ethers, such as diethyl ether, dibutyl ether or ethylene glycol dimethyl ether, alcohols, such as methanol, ethanol, ethylene glycol, monomethyl ether, ketones, amides, sulfoxides or mixtures thereof. Water may also be used in the process according to the present invention.
- The type of polymerization used may be bulk, solution, emulsion, dispersion or suspension polymerization and it may be carried out batchwise, semi-batchwise and continuously.
- Optionally, additives may be added to the polymerization medium before the polymerization or during the polymerization process in order to accelerate the polymerization. Such additives are well-known in the art and are for example camphorsulfonic acid, 2-fluoro-1-methylpyridinium p-toluenesulfonate, acylating compounds such as acetic anhydride (Tetrahedron 1997, 53(45), 15225), glucose, dextrose (Macromolecules 1998, 31, 7559), ascorbic acid (Macromolecules 2001, 34, 6531) or long-life radical initiators as reported in U.S. Pat. No. 6,288,186 (column 4, lines 8-24).
- The polymers prepared according to the present invention show a low polydispersity (Mw/Mn) which is usually lower than 2 and preferably below 1.5.
- The (co)polymers of the present invention may have a number average molecular weight of from 500 to 2·106, preferably from 2000 to 5·105 and more preferably from 2000 to 2.5·105.
- The number average molecular weight of the polymer chains increases linearly with the monomer conversion, which allows a tailor-made polymer molecular weight to be obtained. Furthermore, the molecular weight of the polymers may be controlled by varying the amount of secondary amine(s) and/or oxidizing agent(s) in relation to the amount of monomers. High molecular weight polymers may be formed.
- A further advantage of the present invention is that, after the removal of the non-polymerized monomers from the (co)polymers or after reaching a conversion rate of approximately 100%, a second polymerization step may be initiated simply by adding to the polymer synthesized in the first step a portion of fresh vinyl monomer or monomer mixture that may be different from the vinyl monomer or monomer mixture used in the first polymerization step. The polymerization of the vinyl monomer or monomer mixture added in the second step is then initiated by the polymer chains synthesized in the first polymerization step and di-block copolymers may for example be produced if the polymer chains synthesized in the first polymerization step consist of linear chains with one single growing chain end. The molecular weight and polydispersity of each block may be controlled independently during the respective polymerization step. This process may be repeated several times and may then provide multiblock copolymers of controlled molecular weight and molecular weight distribution for each block.
- The resulting polymers are usually colorless and may be used in most cases without any further purification for the production of coatings, elastomers, adhesives, plastics and compatibilizers in thermoplastic blends.
- The following examples illustrate the invention in more detail.
- The molecular weight was determined by gel permeation chromatography (GPC) using a Shodex RI 74 differential refractometer. A flow rate of 1 ml/min was used and samples were prepared in THF. Polystyrene standards were used for calibration.
- Polymerization of Styrene/Acrylonitrile in the Presence of 2,2,6,6-tetramethylpiperidine and Peracetic Acid, without any Additional Free-Radical Initiator.
- To a 250 ml four-necked round bottomed flask fitted with a mechanical stirrer, a reflux condenser, a thermometer and a funnel is added 1.455 g peracetic acid (Aldrich, 35 wt. %; 0.67 10−2 mol). Then, a mixture of 0.955 g 2,2,6,6-tetramethylpiperidine (Aldrich, 99%; 6.75 10−3 mol), 112.5 g styrene (1.08 mol) and 37.5 g acrylonitrile (0.707 mol) is rapidly added via the funnel. The mixture is stirred and degassed by bubbling through argon for 10 minutes. The reaction medium rapidly becomes pink due to the formation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). After 30 minutes at room temperature, the mixture is heated at reflux for 33 h. Samples are extracted from the reaction flask after 24 and 33 h and dried in vacuo at 70° C. for 24 h. The monomer conversion is determined by gravimetric analysis and the molecular weight of the polymer is determined by GPC. Table 1 shows the results obtained by GPC.
TABLE 1 Results of GPC Time Conversion (h) (%) Mn Mw Mw/Mn 24 37.2 17940 25790 1.43 33 65.7 26660 37530 1.40 - The increase in the molecular weight of the polymer with the monomer conversion and the narrow polydispersity are consistent with a controlled process.
- Polymerization of Styrene/Acrylonitrile in the Presence of 2, 2, 6, 6-tetramethylpiperidine and Peracetic Acid, in the Presence of a Free-Radical Initiator (Benzoyl Peroxide, BPO).
- To a 250 ml four-necked round bottomed flask fitted with a mechanical stirrer, a reflux condenser, a thermometer and a funnel is added 1.455 g peracetic acid (Aldrich, 35 wt. %; 0.67 10−2 mol). Then, a mixture of 0.955 g 2,2,6,6-tetramethylpiperidine (Aldrich, 99%; 6.75 10−3 mol), 1.376 g BPO (5.68 10−3 mol), 112.5 g styrene (1.08 mol) and 37.5 g acrylonitrile (0,707 mol) is rapidly added via the funnel. The mixture is stirred and degassed by bubbling through argon for 10 minutes. The reaction medium rapidly becomes pink due to the formation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). After 30 minutes at room temperature, the mixture is heated under reflux for 1 h. After cooling at room temperature, the polymer is dissolved with chloroform, transferred to an aluminium bag, dried overnight in air and then in vacuo at 70° C. for 24 h. The monomer conversion is determined by gravimetric analysis and the molecular weight of the polymer is determined by GPC. Table 2 shows the results obtained by GPC.
TABLE 2 Results of GPC Time Conversion (h) (%) Mn Mw Mw/Mn 1 77.1 32450 62150 1.91 - In the presence of BPO, the polymerization takes place very rapidly (77% monomer conversion after 1 h) and the polydispersity is very broad (Mw/Mn=1.91), as expected for a conventional uncontrolled polymerization process. Moreover, the polymerization is exothermic and can be dangerous for large scale production.
- Polymerization of Styrene in a One-Pot Process in the Presence of 2,2,6,6-tetramethylpiperidine and m-Chloroperbenzoic Acid (mCPBA), without any Additional Initiator, According to the Present Invention
- To a 250 ml four-necked round-bottomed flask fitted with a mechanical stirrer, a reflux condenser, a thermometer and a funnel is added 4.684 g mCPBA (Acros Organics, 70-75 wt. %; 1,9·10−2 mol). Then, a mixture of 1.342 g 2,2,6,6-tetramethylpiperidine (Aldrich, 99%; 9,5·10−3 mol) and 93.6 g styrene (0.899 mol) are rapidly added via the funnel. The mixture is stirred and degassed by bubbling through argon for 10 minutes. The reaction is slightly exothermic (5-8° C.) and becomes rapidly orange-pink due to the formation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). After 5 h at room temperature, the mixture is heated at 123° C. for 44 h. Samples are extracted from the reaction flask after 10, 20 and 44 h, and dried in vacuo at 70° C. for 24 h. The monomer conversion is determined by gravimetric analysis and the molecular weight of the polymer is determined by GPC. Table 4 shows the results obtained by GPC.
TABLE 4 Results of GPC Time Conversion (h) (%) Mn Mw Mw/Mn 10 10.3 1770 2240 1.26 20 46.0 7680 9870 1.28 44 85.0 11060 16010 1.44 - The increase in the molecular weight of the polymer with the monomer conversion and the narrow polydispersity are consistent with a controlled process.
- Polymerization of Styrene in the Presence of 2, 2,6,6-tetramethylpiperidine and m-chloroperbenzoic Acid (mCPBA):
- a) Polymerization of Styrene in the Presence of 2,2,6,6-tetramethylpiperidine, m-chloroperbenzoic Acid (mCPBA) and Benzoyl Peroxide (BPO)
- Example 1 of U.S. Pat. No. 6,320,007 describes the polymerization of styrene in the presence of 2,2,6,6-tetramethylpiperidine, m-chloroperbenzoic acid (mCPBA) and benzoyl peroxide (BPO) in a three-step process:
- reaction of 2,2,6,6-tetramethylpiperidine with mCPBA for 5 h, for the formation of the corresponding nitroxyl radical (TEMPO);
- a mixture of styrene, BPO and TEMPO (as prepared in the first step) is reacted at 95° C. for 3.5 h. During this period of time, no polymer is formed;
- controlled polymerization occurs by increasing the polymerization temperature to 123° C.
- Polymerization is controlled as shown by the linear evolution of the molecular weight with the monomer conversion and the narrow polydispersity.
- b) Polymerization of Styrene in the Presence of 2,2,6,6-tetramethylpiperidine, m-chloroperbenzoic Acid (mCPBA) and Benzoyl Peroxide (BPO), in a One-Pot Process
- To a 250 ml four-necked round-bottomed flask fitted with a mechanical stirrer, a reflux condenser, a thermometer and a funnel is added 4.684 g mCPBA (Acros Organics, 70-75 wt. %; 1.9 10−2 mol). Then, a mixture of 1.342 g 2,2,6,6-tetramethylpiperidine (Aldrich, 99%; 9.5 10−3 mol), 1.925 g BPO (8 10−3 mol) and 93.6 g styrene (0.899 mol) are rapidly added via the funnel. The mixture is stirred and degassed by bubbling through argon for 10 minutes. The reaction is slightly exothermic (5-8° C.) and the mixture becomes rapidly orange-pink due to the formation of 2,2,6,6-tetra-methylpiperidine-1-oxyl (TEMPO). After 5 h at room temperature, the mixture is heated at 95° C. for 3.5 h. After this period of time, a sample is extracted from the reaction flask for analysis (GPC and monomer conversion). The polymerization medium is then heated at 123° C. and polymerization is terminated after 10 h. The polymer is dried in vacuo at 70° C. for 24 h. The monomer conversion is determined by gravimetric analysis and the molecular weight of the polymer is determined by GPC.
TABLE 3 Results of GPC Temperature Time Conversion (° C.) (h) (%) Mn Mw Mw /Mn 95 3.5 60.2 11920 41800 3.50 123 10 97.7 13010 21400 1.64 - When Example 1 of U.S. Pat. No. 6,320,007 is converted into a one-pot process (all the reagents being added at the beginning of the process), no evolution of the molecular weight with the monomer conversion and broad polydispersity are observed. Additionally, uncontrolled polymerization already occurs when the reaction medium is heated to 95° C.
- Copolymerization of Styrene with n-butyl Acrylate in the Presence of 2,2,6,6-tetramethyl-4-piperidone and Peracetic Acid
- To a 500 ml four-necked round-bottomed flask fitted with a mechanical stirrer, a reflux condenser, a thermometer and a funnel is added 0.7275 g peracetic acid (Aldrich, 35 wt. %; 3,35·10−3 mol). Then, a mixture of 0.5239 g 2,2,6,6-tetra-methyl-4-piperidone (Aldrich, 95%; 3,37·10−3 mol), 75 g styrene (0.72 mol) and 75 g n-butyl acrylate (0.58 mol) are rapidly added via the funnel. The mixture is stirred at room temperature in a water bath and degassed by bubbling through argon for 10 minutes. After 30 minutes at room temperature, the mixture is heated at 110° C. for 1 h, and then at 140° C. Samples are withdrawn from the polymerization medium after 4 and 6 h for analysis. After elimination of the residual monomer, the polymer is dried at 70° C. in vacuo for 24 h.
- After 2 h: Mn=29300; Mw/Mn=1,80; yield=18%
- After 6 h: Mn=42000; Mw/Mn=1,97; yield=48%
- The increase in the molecular weight of the polymer with the monomer conversion is indicative of a controlled process.
- Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (10)
1. A process for producing a polymerized compound selected from the group consisting of oligomer, cooligomer, polymer and copolymer comprising
(I) forming a mixture consisting essentially of
a) at least one monoethylenically unsaturated monomer of the general formula (M),
HR1C═CR2R3 (M)
wherein
R1, R2, R3 independently denote a member selected from the group consisting of hydrogen, C1-C20-alkyl, C1-C20-cycloalkyl C6-C24-aryl, halogen, cyano, C1-C20-alkylester C1-C20-cycloalkylester, C1-C20-alkylamide, C1-C20-cycloalkylamide C6-C24-arylester and C6-C24-arylamide,
b) at least one oxidizing agent (A) and
c) at least one secondary amine of the general formula (I)
wherein
R4 and R5 independently denote a member selected from the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl, C3-C12-heterocycloalkyl, C6-C24-aryl, or C4-C12 alkanol, or
R4 and R5 form, together with the nitrogen atom linking them, a C2-C13-heterocycloalkyl residue containing oxygen, sulfur or nitrogen atoms; or
R4 and R5 together form a residue of a polycyclic ring system or a polycyclic heterocycloaliphatic ring system containing oxygen, sulfur or nitrogen atoms;
wherein the carbon atom of the residue directly adjacent to the nitrogen atom is in each case substituted by 2 or 3 further organic substituents; and
(II) heating the mixture at a polymerization temperature in the range of 0° C. to 220° C.
2. The process of claim 1 wherein each of R4 and R5 independently denotes a first member selected from a first group consisting of C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C3-C12-cycloalkyl, C3-C12-heterocycloalkyl, C6-C24-aryl, which first member is substituted by a second member selected from a second group consisting of NO2, halogen, amino, hydroxy, cyano, carboxy, ester, ketone, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino groups.
3. The process of claim 1 wherein at least one of the residues contains a functional group which is capable of further reacting or crosslinking with functional groups known in the coatings field.
4. The process according to claim 1 , wherein the mixture further contains a solvent selected from the group consisting of water, alcohol, ester, ether, ketone, amide, sulfoxide, hydrocarbon and halogenated hydrocarbon.
5. The process according to claim 1 , wherein monomer (M) is at least one member selected from the group consisting of styrene, substituted styrene, vinyl acetate, acrylonitrile, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and maleic anhydride.
6. The process according to claim 1 , wherein the oxidizing agent (A) is a member selected from the group consisting of peracetic acid, perpropionic acid, hydrogen peroxide, hydrogen peroxide/titanium-containing catalyst, dibenzoyl peroxide, potassium peroxymonosulfate (2 KHSO5.KHSO4.K2SO4), silver oxide and lead (IV) oxide.
7. The process according to claim 1 , wherein the polymerization temperature is between 50 and 180° C.
8. The process according to claim 1 , wherein the polymerization temperature is between 70 and 150° C.
9. The process according to claim 1 , wherein the temperature in step (I) is between 0 and 100° C.
10. The process according to claim 1 , wherein the temperature in step (I) is between 0 and 50° C.
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EP02027694A EP1428838A1 (en) | 2002-12-13 | 2002-12-13 | In situ-polymerization of monoethylenically unsaturated monomers with secondary amines |
EP02027694.5 | 2002-12-13 |
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EP (1) | EP1428838A1 (en) |
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US3287298A (en) * | 1962-12-28 | 1966-11-22 | Dal Mon Research Co | Oxygen-convertible block copolymers of polymeric dianions |
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US4581429A (en) * | 1983-07-11 | 1986-04-08 | Commonwealth Scientific And Industrial Research Organization | Polymerization process and polymers produced thereby |
US5919871A (en) * | 1995-02-07 | 1999-07-06 | Elf Atochem S.A. | Stabilization of a polymer by a stable free radical |
US6262179B1 (en) * | 1995-02-07 | 2001-07-17 | Atofina | Process for the manufacture of a composition comprising a vinylaromatic polymer and a rubber by polymerization in the presence of a stable free radical |
US6262206B1 (en) * | 1997-07-15 | 2001-07-17 | Ciba Specialty Chemicals Corporation | Polymerizable compositions containing alkoxyamine compounds derived from nitroso- or nitrone compounds |
US6320007B1 (en) * | 1994-11-18 | 2001-11-20 | Xerox Corporation | Process for producing thermoplastic resin polymers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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AU571240B2 (en) * | 1983-07-11 | 1988-04-14 | Commonwealth Scientific And Industrial Research Organisation | Alkoxy-amines, useful as initiators |
-
2002
- 2002-12-13 EP EP02027694A patent/EP1428838A1/en not_active Withdrawn
-
2003
- 2003-12-10 MX MXPA03011446A patent/MXPA03011446A/en not_active Application Discontinuation
- 2003-12-10 US US10/732,592 patent/US20040122270A1/en not_active Abandoned
- 2003-12-10 CA CA002452970A patent/CA2452970A1/en not_active Abandoned
- 2003-12-12 KR KR1020030090476A patent/KR20040055588A/en not_active Application Discontinuation
- 2003-12-12 JP JP2003414877A patent/JP2004197092A/en active Pending
- 2003-12-15 CN CNA2003101206022A patent/CN1506379A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2557363A (en) * | 1944-12-30 | 1951-06-19 | Standard Oil Dev Co | Amine activated polymerization process |
US3287298A (en) * | 1962-12-28 | 1966-11-22 | Dal Mon Research Co | Oxygen-convertible block copolymers of polymeric dianions |
US3485894A (en) * | 1964-01-20 | 1969-12-23 | Shell Oil Co | Interpolymers of vinyl arenes and certain block copolymers and process for their preparation |
US3726837A (en) * | 1969-07-08 | 1973-04-10 | Akzo Nv | Polymerization of ethylenically unsaturated monomers with a 1,2-diaryl-1,2-dicyano-ethane |
US4581429A (en) * | 1983-07-11 | 1986-04-08 | Commonwealth Scientific And Industrial Research Organization | Polymerization process and polymers produced thereby |
US6320007B1 (en) * | 1994-11-18 | 2001-11-20 | Xerox Corporation | Process for producing thermoplastic resin polymers |
US5919871A (en) * | 1995-02-07 | 1999-07-06 | Elf Atochem S.A. | Stabilization of a polymer by a stable free radical |
US6255448B1 (en) * | 1995-02-07 | 2001-07-03 | Atofina | Polymerization in the presence of a β-substituted nitroxide radical |
US6262179B1 (en) * | 1995-02-07 | 2001-07-17 | Atofina | Process for the manufacture of a composition comprising a vinylaromatic polymer and a rubber by polymerization in the presence of a stable free radical |
US6262206B1 (en) * | 1997-07-15 | 2001-07-17 | Ciba Specialty Chemicals Corporation | Polymerizable compositions containing alkoxyamine compounds derived from nitroso- or nitrone compounds |
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EP1428838A1 (en) | 2004-06-16 |
JP2004197092A (en) | 2004-07-15 |
KR20040055588A (en) | 2004-06-26 |
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